Electrical conductivity, ion-molecular and interionic interactions in solutions of some tetraalkylammonium salts in acetonitrile: the influence of the ion and temperature
Conductance data for Et4NBr, Et4NBF4, Bu4NBr, Bu4NBF4 in acetonitrile for the molar concentration range of 2·10-4–1·10-2 mol·dm-3 over the temperature range from 5 to 55 °C are reported. Limiting molar conductivities and ion association constants were determined by using the Lee-Wheaton equation for the symmetrical electrolytes. On the basis of the preliminary conductometric data analysis it was established that the closest approach parameter is almost independent from the temperature for all studied acetonitrile solutions. Therefore, the closest approach parameter was adopted as a sum of cation and anion radii for further conductometric data treatment.
The limiting conductivities of Br-, BF4-, Et4N+ and Bu4N+ ions and the structure-dynamic parameter of ion-molecular interaction obtained from the experimental data on limiting molar conductivities were evaluated in the framework of the approach proposed by authors [Kalugin O. N., Vjunnik I. N. Limiting ion conductance and dynamic structure of the solvent in electrolyte solution. Zh. Khim. Fiz. (Rus.) 1991, 10 708-714]. Elongation of the alkyl radical of the tetraalkylammonium cation from Et4N+ to Bu4N+ leads to a significant increase in the structure-dynamic parameter, which indicates the dynamic structuring of the solvent near the tetrabutylammonium ion and increased solvophobic solvation of the Bu4N+ compared to Et4N+.
Ion association constants are discussed in terms of competition between Coulomb and non-Coulomb forces in terms of short-range square-mound potential. An increase in the ion association constants in the sequence Bu4NBF4<Et4NBF4<Bu4NBr<Et4NBr was explained by the increase in the contribution of short-range ion-molecular interactions to the interionic attraction in addition to the electrostatic component. An increase in temperature enhances the ionic association due to both the electrostatic and short-range components.
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